Synthesis of biobased and substituted terephthalic acids and isophthalic acids

1. A method for producing terephthalic acid, isophthalic acid or both terephthalic acid and isophthalic acid, comprising:

(a) reacting isoprene with acrylic acid in the presence of a first catalyst to form a first product selected from the group consisting of 4-methyl-3-cyclohexene-1-carboxylic acid, 3-methyl-3-cyclohexene-1-carboxylic acid, and mixtures thereof;

(b) performing an aromatization reaction on the first product to form a second product selected from the group consisting of para-toluic acid, meta-toluic acid, and mixtures thereof; and

(c) performing an oxidation reaction on the second product in the presence of a third catalyst to form terephthalic acid, isophthalic acid, or mixtures thereof.

2. The method according to claim 1 , wherein the first catalyst is a Lewis acid catalyst, wherein the Lewis acid catalyst comprises an aluminum, copper, hafnium, magnesium, nickel, iron, yttrium, zinc, zirconium, scandium, tin, or titanium cation, and comprises a triflates, chlorides, or bromides counterion.

3. The method according to claim 2 , wherein the Lewis acid catalyst is selected from the group consisting of CuCl, CuCl 2 , NiCl 2 , YCl 3 , FeCl 2 , AlCl 3 , FeCl 3 , ZnCl 2 , MgCl 2 , TiCl 3 , SnCl 4 , ScCl 3 , SnCl 2 , HfCl 4 , ZrCl 4 , and TiCl 4 .

4. The method according to claim 1 , wherein the reaction of the isoprene with the acrylic acid is performed under neat conditions.

5. The method according to claim 1 , wherein the reaction is maintained at room temperature for from about 1 hour to about 48 hours.

6. The method according to claim 1 , wherein the reaction is maintained at from about −20° C. to about 30° C. for from about 48 hours to about 100 hours.

7. The method according to claim 1 , wherein the first catalyst is boronic acid or 2-bromophenyl boronic acid.

8. The method according to claim 1 , wherein the aromatization reaction is conducted in the presence of sulfuric acid or acetic anhydride solvent.

9. The method according to claim 1 , wherein the aromatization reaction is conducted in the presence of a catalyst selected from the group consisting of chromium, molybdenum, iridium, rhodium, ruthenium, nickel, palladium, platinum, vanadium, iron and manganese.

10. The method according to claim 1 , wherein the aromatization reaction is a vapor phase dehydrogenation conducted using a second catalyst, optionally selected from the group consisting of chromium, molybdenum, iridium, rhodium, ruthenium, nickel, palladium, and platinum.

11. The method according to claim 10 , wherein the second catalyst is a Pd on C catalyst and the bio-4-methyl-3-cyclohexene-1-carboxylic acid, bio-3-methyl-3-cyclohexene-1-carboxylic acid, or mixture thereof is distilled at from about 50 mm to about 100 mm and from about 100° C. to about 300° C. through the Pd on C catalyst dispersed in macroporous silica gel.

12. The method according to claim 1 , wherein the third catalyst is a Co(OAc) 2 /Mn(OAc) 2 catalyst in acetic acid solvent.

13. The method according to claim 1 , wherein the third catalyst is an N-hydroxyimide catalyst, preferably selected from the group consisting of N-hydroxyphthalimide (NHPI), N-hydroxysuccinimide (NHSI), N-hydroxy-1,8-naphthalimide (NHNI), and carbonic acid tert-butyl phthalimido ester (CATPE).

14. The method according to claim 1 , wherein one or both of the isoprene and the acrylic acid are bio-based.

15. A method for producing a substituted bio-terephthalates and/or substituted bio-isophthalates comprising:

(a) reacting bio-isoprene, with a substituted bio-alkene to form a first bio-product;

(b) aromatizing the first bio-product to form a second bio-product; and

(c) oxidizing the second bio-product to form the substituted bio-terephthalate and/or substituted bio-isophthalate.

16. The method according to claim 15 , wherein the substituted bio-alkene is bio-cinnamic acid, bio-fumaric acid, or bio-maleic acid.

17. A method for producing terephthalic acid and/or isophthalic acid, and derivatives thereof, comprising:

(a) performing a neat cycloaddition reaction by reacting bio-isoprene with a bio-dienophile in the presence of a TiCl 4 catalyst to form a first bio-product;

(b) performing an aromatization on the first product to form a second bio-product by distilling the first product with a Pd(0) on C catalyst to generate the second product; and

(c) performing an oxidation reaction on the second bio-product, by reacting the second bio-product with a Co(OAc) 2 /Mn(OAc) 2 catalyst in acetic acid with a N-hydroxysuccinimide radical chain carrier, form bio-terephthalic acid, bio-isophthalic acid, or combinations thereof.

18. The method according to claim 17 , wherein the cycloaddition reaction and is conducted at about ambient temperature.

19. The method according to claim 17 , wherein the bio-dienophile is bio-acrylic acid.

20. A method of making poly(ethylene terephthalate) comprising:

(a) reacting isoprene with acrylic acid in the presence of a first catalyst to produce 4-methyl-3-cyclohexene-1-carboxylic acid and 3-methyl-3-cyclohexene-1-carboxylic acid;

(b) performing an aromatization reaction on the 4-methyl-3-cyclohexene-1-carboxylic acid and the 3-methyl-3-cyclohexene-1-carboxylic acid to produce para-toluic acid and meta-toluic acid;

(c) performing an oxidation reaction on the para-toluic acid and the meta-toluic acid in the presence of a third catalyst to form terephthalic acid and isophthalic acid; and

(d) polymerizing the terephthalic acid and the isophthalic acid with ethylene glycol to produce poly(ethylene terephthalate).

21. The method of claim 20 , wherein one or both of the isoprene and acrylic acid are bio-based.